EP1188775B1 - Méthode de préparation d'une émulsion d'une résine ester polyvinylique - Google Patents
Méthode de préparation d'une émulsion d'une résine ester polyvinylique Download PDFInfo
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- EP1188775B1 EP1188775B1 EP01307887A EP01307887A EP1188775B1 EP 1188775 B1 EP1188775 B1 EP 1188775B1 EP 01307887 A EP01307887 A EP 01307887A EP 01307887 A EP01307887 A EP 01307887A EP 1188775 B1 EP1188775 B1 EP 1188775B1
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- European Patent Office
- Prior art keywords
- emulsion
- water
- ethylene
- polymerization
- polyvinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Definitions
- the present invention relates to a method for producing a polyvinyl ester resin emulsion which has high viscosity and has good water resistant adhesiveness, heat-resistant adhesiveness, hot water-resistant adhesiveness and storage stability, especially high-temperature storage stability, and which has good film-forming ability and is readily formed into transparent films.
- polyvinyl alcohol (hereinafter referred to as PVA) is widely used as a protective colloid in the emulsion polymerization of an ethylenic unsaturated monomer, especially a vinyl ester monomer such as vinyl acetate.
- Aqueous emulsions of polyvinyl ester resins obtained through emulsion polymerization with PVA serving as a protective colloid have many applications in various fields of adhesives for paper products, wood products, plastics, etc., binders for dip-coated paper, non-woven fabrics, etc., as well as admixtures, jointing agents, coating compositions, paper processing agents, fiber processing agents, etc.
- aqueous emulsions containing PVA have many applications in various fields.
- aqueous emulsions of polyvinyl esters that contain partially-hydrolyzed PVA serving as a protective colloid are widely used.
- Such aqueous emulsions of polyvinyl esters that contain partially-hydrolyzed PVA serving as protective colloid have good low-temperature storage stability and their viscosity can be increased with ease, but they have a problem in that their water resistance is poor.
- aqueous emulsions of polyvinyl esters that contain completely-hydrolyzed PVA serving as a protective colloid have good water resistance, but have a problem in that their low-temperature storage stability is not good.
- the inventors of Japanese Patent Laid-Open Nos. 46252/1988 and 62347/1989 have proposed a technique of adding 3-methyl-3-methoxybutanol or a water-soluble compound having an alcoholic OH group to such aqueous emulsions, and they have succeeded in improving the water resistance and the storage stability of the resulting aqueous emulsions.
- the aqueous emulsions proposed contain a water-soluble compound added thereto, their water resistance is limited, and, in addition, since their plasticizability (which is indispensable to polyvinyl acetate emulsions) is poor, they require the presence of a plasticizer.
- the inventors of Japanese Patent Laid-Open Nos. 21529/1999, 21380/1999 and 226774/1998 have proposed a technique of using, as a dispersant, polyvinyl alcohol having ethylene units in emulsions such as those discussed herein, and they have succeeded in significantly improving the water resistance and the low-temperature storage stability of the emulsions that contain the dispersant.
- the solubility in water of the polyvinyl alcohol having ethylene units is lowered by the ethylene units introduced into the polymer. Therefore, the emulsions that contain the polyvinyl alcohol serving as protective colloid have a problem in that they are greatly thickened when produced through emulsion polymerization at 60 to 80°C.
- emulsions are greatly thickened when they are produced through emulsion polymerization, they cannot be well stirred and therefore cannot be good emulsions.
- the solid content of the emulsions must be lowered in order that the emulsions produced can be well stirred even at high temperatures.
- the emulsions thus produced inevitably have low viscosity, and are therefore unsuitable adhesives for wood products that require high viscosity.
- the emulsions produced are also thickened at high temperatures of 40°C or higher, and their high-temperature storage stability is not good.
- Emulsions that contain such polyvinyl alcohol having ethylene units serving as protective colloid have good low-temperature storage stability. Therefore, completely-hydrolyzed, polyvinyl alcohol products having ethylene units are also being used in the field in which partially-hydrolyzed PVA has heretofore been used.
- the interfacial activity of the completely-hydrolyzed PVA is lower than that of the conventional partially-hydrolyzed PVA, and therefore the particle size of the emulsions that contain the completely-hydrolyzed PVA will be large. As their particle size is large, the emulsionsnare problematic in that the films formed from them cannot be transparent.
- the present invention seeks to provide a polyvinyl ester resin emulsion which has high viscosity and has good water resistant adhesiveness, heat-resistant adhesiveness, hot water-resistant adhesiveness and storage stability, especially high-temperature storage stability, and which has good film-forming ability and is readily formed into transparent films.
- the present inventors have assiduously sought to develop such a polyvinyl ester resin emulsion having the above properties, and, as a result, have found that a polyvinyl ester resin emulsion produced through emulsion polymerization of a vinyl ester monomer in the presence of a polyvinyl alcohol serving as protective colloid and in the presence of a water-insoluble, hydroxyl group-containing compound satisfies the above-mentioned object.
- the inventors have also found that, when a polyvinyl alcohol containing from 0.5 mol% to 20 mol% of ethylene units is used in the method of emulsion polymerization, then the properties of the polyvinyl ester resin emulsion produced therein are further improved.
- the polyvinyl alcohol for use in the invention (hereinafter referred to as PVA polymer) is not specifically defined in terms of its production, and it may be produced by any known method of hydrolyzing vinyl ester polymers.
- the polyvinyl alcohol containing from 0.5 mol% to 20 mol% of ethylene units, which may be used in the invention (hereinafter referred to as PVA polymer of low ethylene modification, or low-ethylene PVA polymer), is also not specifically defined in terms of its production, and it may be produced by any known method of hydrolyzing vinyl ester-ethylene copolymers.
- the dispersant i.e. the PVA polymer
- the ethylenic unsaturated comonomer includes, for example, propylene, acrylic acid, methacrylic acid, fumaric acid, maleic acid (anhydride), acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, trimethyl-(3-acrylamido-3-dimethylpropyl)-ammonium chloride, acrylamido-2-methylpropanesulfonic acid and its sodium salt, ethyl vinyl ether, butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, sodium vinylsulfonate, sodium allylsulfonate, as well as N
- Copolymerizing the vinyl ester monomer with ethylene to form an ethylene-vinyl ester resin emulsion is one preferred embodiment of the invention.
- the ethylene content of the ethylene-vinyl ester resin emulsion is not specifically defined, and may generally fall between 3 and 35 % by weight.
- the ethylene-vinyl ester resin emulsion of which the ethylene content falls withinthis range has more improved water resistant adhesiveness and heat-resistant adhesiveness.
- the dispersoid may be a copolymer with any other copolymerizable ethylenic unsaturated monomer or dienic monomer. It may contain at least one monomer unit selected from ethylenic unsaturated monomers and dienic monomers, and the comonomers include, for example, olefins such as propylene, isobutylene, etc.; olefin halides such as vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, etc.; acrylic acid, methacrylic acid; acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, 2-hydroxyethyl acrylate, etc.; methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethy
- the water-insoluble, hydroxyl group-containing compound to be used in the emulsion polymerization of a vinyl ester monomer in accordance with the invention is insoluble in water and has a hydroxyl group.
- the terminology, water-insoluble or insoluble in water referred to herein is meant to indicate that the saturation solubility in water of the water-insoluble, hydroxyl group-containing compound is at most 8 g in 100 cc of water at 60°C.
- One preferred example of the water-insoluble, hydroxyl group-containing compound is a water-insoluble ester alcohol compound.
- the water-insoluble ester alcohol compound is an aliphatic ester alcohol compound having both an ester group and a hydroxyl group that is prepared through reaction of a polyalcohol, e.g., glycol, with an aliphatic carboxylic acid.
- a polyalcohol e.g., glycol
- aliphatic monocarboxylic acids including, for example, acetic acid, propionic acid, formic acid, pivalic acid, caproic acid, hexanoic acid, heptanoic acid, nonanoic acid, decanoic acid, etc.
- the aliphatic ester alcohol compound has from 5 to 80 carbon atoms, more preferably from 6 to 60 carbon atoms in total.
- propylene glycol mono-2-ethylhexanoate polypropylene glycol mono-2-ethylhexanoate, propylene glycol mono-2-methylhexanoate, propylene glycol mono-2-ethylpropanoate, ethylene glycol mono-2-ethylhexanoate, polyethylene glycol mono-2-ethylhexanoate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, etc.
- propylene glycol mono-2-ethylhexanoate and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate which are available on the market.
- the mean particle size of the polyvinyl ester resin emulsion of the invention is not specifically defined, but in general, it is preferably at most 1 ⁇ m measured according to a dynamic light-scattering method, more preferably at most 0.8 ⁇ m. Having a mean particle size that falls within the defined range, the emulsion can form films of higher transparency.
- a laser zeta potentiometer is used, for example, Otuka Electronics' ELS-8000.
- the solid content of the polyvinyl ester resin emulsion of the invention is not specifically defined, but generally falls between 30 and 70 % by weight, preferably between 40 and 65 % by weight. If its solid content is smaller than 30 % by weight, the emulsion will lose storage stability, and will be separated into two phases; but if larger than 70 % by weight, the emulsion will be difficult to produce.
- the monomer is put into the reactor all at one time or continuously, and a polymerization initiator, for example, an azo-type polymerization initiator or a peroxide-type polymerization initiator such as hydrogen peroxide, ammonium persulfate or potassium persulfate is added thereto, and the monomer is thereby polymerized in a mode of emulsion polymerization.
- a polymerization initiator for example, an azo-type polymerization initiator or a peroxide-type polymerization initiator such as hydrogen peroxide, ammonium persulfate or potassium persulfate is added thereto, and the monomer is thereby polymerized in a mode of emulsion polymerization.
- the polymerization initiator, hydrogen peroxide may be combined with any of tartaric acid, L-ascorbic acid, Rongalit or the like; and ammonium persulfate and potassium persulfate may be combined with any of sodium hydrogensulfite, sodium hydrogencarbonate or the like.
- the polyvinyl ester resin emulsion obtained in the invention has high viscosity and has good water resistant adhesiveness, heat-resistant adhesiveness, hot water-resistant adhesiveness and storage stability, especially high-temperature storage stability, and, in addition, it has good film-forming ability and is readily formed into transparent films. Therefore, the emulsion is favorable for various types of adhesives, for example, for adhesives for wood products, adhesives for paper products and adhesives for plywood/polyvinyl chloride laminates, and is especially favorable for wood-processing adhesives that require high viscosity.
- the emulsion is also favorably used in other various fields, for example, binders for dip-coated paper, non-woven fabrics, etc., as well as admixtures, jointing agents, paints, paper processing agents, fiber processing agents, coating agents, etc.
- the polyvinyl ester resin emulsion obtained is applied onto a piece of straight-grained birch lumber in an amount of 150 g/m 2 , and this is stuck on another piece of the same lumber.
- the two with the emulsion therebetween are pressed under a pressure of 7 kg/m 2 for 16 hours. After releasing from the pressure, this is cured at 20°C and 65 % RH for 5 days.
- the test piece is then left in a drier at 60°C for 24 hours, and immediately after having been thus left therein, its compression shear strength is measured at 20°C and 65 % RH.
- the polyvinyl ester resin emulsion obtained is applied onto a piece of straight-grained birch lumber in an amount of 150 g/m 2 , and this is stuck on another piece of the same lumber.
- the two with the emulsion therebetween are pressed under a pressure of 7 kg/m 2 for 16 hours. After released from the pressure, this is cured at 20°C and 65 % RH for 5 days. Next, this is immersed in warm water at 60°C for 3 hours. While still wet, the compression shear strength of the test piece is measured.
- the emulsion is left at 60°C for 1 month, and, after having been thus left, its condition is checked.
- Table 1 “O” indicates no change of the sample tested; “ ⁇ ” indicates that the viscosity of the sample tested increased a little; and “ ⁇ ” indicates that the sample tested gelled.
- the emulsion is cast at 20°C into a film having a thickness of 500 ⁇ m, and the film is checked as to whether or not it is transparent.
- Table 1 “O” indicates that the film is almost transparent; “ ⁇ ” indicates that the film is somewhat cloudy; and “ ⁇ ” indicates that the film is entirely cloudy.
- the mean particle size of the emulsion is measured according to a dynamic light-scattering method.
- a polyvinyl acetate emulsion having a solid content of 47.9 % was produced according to the same process of emulsion polymerization as in Example 1, except that 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Chisso's CS-12, having a saturation solubility of 0.15 g) and not propylene glycol mono-2-ethylhexanoate in Example 1 was used herein. Its properties were evaluated in the same manner as in Example 1. The results are given in Table 1.
- a polyvinyl acetate emulsion having a solid content of 47.6 % was produced according to the same process of emulsion polymerization as in Example 1, except that propylene glycol mono-2-ethylhexanoate was added to the reaction system not before the start of emulsion polymerization but after the step of emulsion polymerization. Its properties were evaluated in the same manner as in Example 1. The results are given in Table 1.
- a polyvinyl acetate emulsion having a solid content of 47.9 % was produced according to the same process of emulsion polymerization as in Example 1, except that PVA-4 (having a degree of polymerization of 1000, a degree of hydrolysis of 99.2 mol%, and a degree of ethylene modification of 8 mol%) and not PVA-1 in Example 1 was used herein. Its properties were evaluated in the same manner as in Example 1. The results are given in Table 1.
- a polyvinyl acetate emulsion having a solid content of 47.9 % was produced according to the same process of emulsion polymerization as in Example 1, except that not propylene glycol mono-2-ethylhexanoate (Yokkaichi Chemical's Waijinol EHP01) used in Example 1 but the same amount of ion-exchanged water was used herein. Its properties were evaluated in the same manner as in Example 1. The results are given in Table 1.
- a polyvinyl acetate emulsion having a solid content of 47.5 % was produced according to the same process of emulsion polymerization as in Example 1, except that not propylene glycol mono-2-ethylhexanoate (Yokkaichi Chemical's Waijinol EHP01) used in Example 1 but the same amount of 3-methoxy-3-methyl-1-butanol (Kuraray's MMB, having a saturation solubility of at least 100 g) was used herein. Its properties were evaluated in the same manner as in Example 1. The results are given in Table 1.
- An ethylene-vinyl acetate resin emulsion having a solid content of 55.2 % was produced according to the same process of emulsion polymerization as in Example 6, except that not propylene glycol mono-2-ethylhexanoate (Yokkaichi Chemical's Waijinol EHP01) used in Example 6 but the same amount of ion-exchanged water was used herein.
- the ethylene content of the copolymer resin was 20 % by weight.
- the properties of the emulsion were evaluated in the same manner as in Example 1. The results are given in Table 1.
- a polyvinyl acetate emulsion having a solid content of 47.7 % was produced according to the same process of emulsion polymerization as in Example 1, except that not propylene glycol mono-2-ethylhexanoate (Yokkaichi Chemical's Waijinol EHP01) used in Example 1 but the same amount of ion-exchanged water was used herein.
- propylene glycol mono-2-ethylhexanoate Yokkaichi Chemical's Waijinol EHP01
- the results are given in Table 1.
- a polyvinyl acetate emulsion having a solid content of 47.7 % was produced according to the same process of emulsion polymerization as in Example 7, except that PVA-1 (Kuraray's PVA-117, having a degree of polymerization of 1700 and a degree of hydrolysis of 98.5 mol%) and not PVA-5 in Example 7 was used herein. Its properties were evaluated in the same manner as in Example 7. The results are given in Table 2.
- a polyvinyl acetate emulsion having a solid content of 47.8 % was produced according to the same process of emulsion polymerization as in Example 10, except that ethylene glycol monophenyl ether used in Example 10 was not used herein. Its properties were evaluated in the same manner as in Example 7. The results are given in Table 2.
- a polyvinyl acetate emulsion having a solid content of 47.9 % was produced according to the same process of emulsion polymerization as in Example 7, except that PVA-4 (having a degree of polymerization of 1000, a degree of hydrolysis of 99.2 mol%, and a degree of ethylene modification of 8 mol%) and not PVA-5 in Example 7 was used herein. Its properties were evaluated in the same manner as in Example 7. The results are given in Table 2.
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- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paints Or Removers (AREA)
Claims (7)
- Procédé pour produire une émulsion de résine ester polyvinylique, qui comprend de polymériser un monomère ester vinylique par polymérisation en émulsion en présence d'un alcool polyvinylique servant de colloïde protecteur et en présence d'un composé contenant un groupe hydroxyle, insoluble dans l'eau ayant une solubilité de saturation d'au plus 8 g dans 100 cm3 d'eau à 60°C, et dans lequel le composé insoluble dans l'eau est choisi dans le groupe consistant en : un composé ester alcool insoluble dans l'eau formé par la réaction d'un polyalcool avec un acide carboxylique aliphatique ayant de 1 à 30 atomes de carbone et dans lequel le polyalcool est choisi dans le groupe consistant en éthylène glycol, propylène glycol, diéthylène glycol, polypropylène glycol, polyéthylène glycol, glycérine, 1,3-butylène glycol, triméthylolpropane et 2,2,4-triméthyl-1,3-pentane diol ; éther monophénylique d'éthylène glycol ; éther monophénylique de diéthylène glycol ; éther monophénylique de polyéthylène glycol ; et éther monophénylique de propylène glycol.
- Procédé selon la revendication 1, dans lequel l'alcool polyvinylique contient de 0,5% en moles à 20% en moles d'unités éthylène.
- Procédé selon la revendication 1 ou la revendication 2, dans lequel l'émulsion de résine ester polyvinylique est une émulsion d'un copolymère d'un monomère ester vinylique et d'éthylène.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le composé ester alcool insoluble dans l'eau est le mono-2-éthylhexanoate de propylène glycol.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le composé ester alcool insoluble dans l'eau est le monoisobutyrate de 2,2,4-triméthyl-1,3-pentanediol.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le diamètre moyen de particule de l'émulsion de résine ester polyvinylique est au plus 1 µm mesuré selon une méthode par diffusion dynamique de la lumière.
- Adhésif qui comprend une émulsion de résine ester polyvinylique obtenue selon le procédé de la revendication 1.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP2000283311 | 2000-09-19 | ||
JP2000283311 | 2000-09-19 | ||
JP2001038091 | 2001-02-15 | ||
JP2001038091A JP2002167403A (ja) | 2000-09-19 | 2001-02-15 | ビニルエステル系樹脂エマルジョンの製法 |
Publications (3)
Publication Number | Publication Date |
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EP1188775A2 EP1188775A2 (fr) | 2002-03-20 |
EP1188775A3 EP1188775A3 (fr) | 2002-10-09 |
EP1188775B1 true EP1188775B1 (fr) | 2005-11-16 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP01307887A Expired - Lifetime EP1188775B1 (fr) | 2000-09-19 | 2001-09-17 | Méthode de préparation d'une émulsion d'une résine ester polyvinylique |
Country Status (7)
Country | Link |
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US (1) | US6780931B2 (fr) |
EP (1) | EP1188775B1 (fr) |
JP (1) | JP2002167403A (fr) |
KR (1) | KR100478969B1 (fr) |
CN (1) | CN1165554C (fr) |
DE (1) | DE60114959T2 (fr) |
TW (1) | TW583198B (fr) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6964990B2 (en) | 1999-12-16 | 2005-11-15 | Kuraray Co., Ltd. | Ethylene-vinyl alcohol copolymer resin composition of improved long-run workability, and its shaped articles |
JP4615133B2 (ja) * | 2001-02-16 | 2011-01-19 | 株式会社クラレ | ビニルエステル系樹脂エマルジョンの製法 |
US7981958B1 (en) * | 2002-09-17 | 2011-07-19 | Kuraray Co., Ltd. | Synthetic resin emulsion powder |
ES2337686T3 (es) * | 2003-04-09 | 2010-04-28 | Kuraray Co., Ltd. | Emulsion de resina (met)acrilica y procedimiento para produccion de la misma. |
CN100360569C (zh) * | 2003-04-09 | 2008-01-09 | 可乐丽股份有限公司 | (甲基)丙烯酸树脂系乳状液及其制造方法 |
KR100830909B1 (ko) * | 2007-04-27 | 2008-05-22 | (주)영우켐텍 | 아크릴산 에스테르 공중합체 조성물 및 재분산성 분말 |
CA2689182A1 (fr) * | 2008-12-29 | 2010-06-29 | Alistair John Mclennan | Copolymeres d'acetate de vinyle et de neoalcanoate de vinyle et leurs utilisations |
KR20110128792A (ko) | 2008-12-29 | 2011-11-30 | 셀라니즈 이멀젼스 게엠베하 | 보강 섬유용 사이징제로서 사용되는 알킬 메타크릴레이트/알킬 아크릴레이트 공중합체 |
CN101798367A (zh) * | 2008-12-29 | 2010-08-11 | 赛拉尼斯乳胶有限公司 | 乙酸乙烯基酯/丁烯二酸环烷基酯共聚物及其用途 |
EP2204390A3 (fr) * | 2008-12-29 | 2010-07-28 | Celanese Emulsions GmbH | Résines de liaison de copolymère d'acétate de vinyle/ester vinylique aromatique |
IT1399630B1 (it) | 2010-04-20 | 2013-04-26 | Perfetti Van Melle Spa | Formulazioni alimentari a lento rilascio |
CA2743794C (fr) * | 2010-06-25 | 2013-09-10 | Dow Global Technologies Llc | Coalescent pour les compositions aqueuses |
RU2469541C2 (ru) * | 2011-03-30 | 2012-12-20 | Общество С Ограниченной Ответственностью "Производственно-Коммерческая Фирма "Атлантис-Пак" | Модифицированный поливиниловый спирт и содержащая его паро- и дымопроницаемая синтетическая оболочка для пищевых продуктов |
EP2756012B1 (fr) | 2011-09-12 | 2016-01-13 | OXEA GmbH | Résines liantes à base d'un copolymère acétate de vinyle/3,5,5-triméthylhexanoate de vinyle |
CN104837939B (zh) * | 2012-12-14 | 2019-01-08 | 汉高股份有限及两合公司 | 用于制备聚乙酸乙烯酯分散体的方法 |
US9963557B2 (en) | 2015-05-27 | 2018-05-08 | Dow Global Technologies Llc | Low-VOC, low cost coalescent for certain aqueous polymeric dispersions |
CN113072170B (zh) * | 2021-04-22 | 2022-09-13 | 青海洁神环境科技股份有限公司 | 一种生物转盘盘片材料及其制备方法 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2662866A (en) * | 1950-08-12 | 1953-12-15 | Du Pont | Emulsion polymerization of vinyl acetate |
DE3226681A1 (de) * | 1982-07-16 | 1984-01-19 | Hoechst Ag, 6230 Frankfurt | Waessrige polyvinylester-dispersion, verfahren zu ihrer herstellung und ihre verwendung |
US4921898A (en) | 1985-08-02 | 1990-05-01 | Air Products And Chemicals, Inc. | Vinyl acetate-ethylene copolymer emulsions prepared in the presence of a stabilizing system of a low molecular weight polyvinyl alcohol and a surfactant |
JPH0618966B2 (ja) | 1986-08-14 | 1994-03-16 | コニシ株式会社 | 酢酸ビニル樹脂エマルジヨン組成物 |
JPH086003B2 (ja) | 1987-09-01 | 1996-01-24 | コニシ株式会社 | 酢酸ビニル樹脂エマルジョン組成物 |
CA2027985A1 (fr) * | 1989-10-27 | 1991-04-28 | Koichiro Saeki | Adhesif en deux parts pour le bois |
GB9109483D0 (en) * | 1991-05-02 | 1991-06-26 | Shell Int Research | Interpolymer latices from vinyl acetate and vinyl esters of branched chain carboxylic acids |
CA2144792C (fr) | 1994-07-14 | 2000-05-02 | Masato Nakamae | Emulsion aqueuse |
DE4431343A1 (de) * | 1994-09-02 | 1996-03-07 | Hoechst Ag | Heterogene Polyvinylester-Dispersionen und -Pulver |
KR970059189A (ko) * | 1996-01-31 | 1997-08-12 | 글렌 디. 푸게이트 | 유화 중합반응 분산액 중의 셀룰로즈 에테르 |
US5834538A (en) * | 1996-06-18 | 1998-11-10 | Hercules Incorporated | Pressure sensitive adhesives |
TW454015B (en) * | 1996-10-07 | 2001-09-11 | Kuraray Co | Water resistant composition |
JPH10226774A (ja) | 1997-02-14 | 1998-08-25 | Kuraray Co Ltd | 水性エマルジョン型接着剤 |
JPH1121529A (ja) | 1997-06-30 | 1999-01-26 | Kuraray Co Ltd | 水性エマルジョン型接着剤 |
JP3630925B2 (ja) | 1997-06-30 | 2005-03-23 | 株式会社クラレ | 水性エマルジョン |
US6300403B1 (en) * | 1997-09-26 | 2001-10-09 | Wacker-Chemie Gmbh | Method for producing polymers stabilized with protective colloids |
US6156840A (en) * | 1998-01-26 | 2000-12-05 | Kuraray Co., Ltd. | Method for producing aqueous emulsion of polyurethane |
-
2001
- 2001-02-15 JP JP2001038091A patent/JP2002167403A/ja not_active Withdrawn
- 2001-08-28 US US09/939,811 patent/US6780931B2/en not_active Expired - Fee Related
- 2001-09-14 TW TW090122847A patent/TW583198B/zh not_active IP Right Cessation
- 2001-09-17 EP EP01307887A patent/EP1188775B1/fr not_active Expired - Lifetime
- 2001-09-17 DE DE60114959T patent/DE60114959T2/de not_active Expired - Lifetime
- 2001-09-18 KR KR10-2001-0057677A patent/KR100478969B1/ko not_active IP Right Cessation
- 2001-09-19 CN CNB011331550A patent/CN1165554C/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN1165554C (zh) | 2004-09-08 |
KR20020022592A (ko) | 2002-03-27 |
US20020065361A1 (en) | 2002-05-30 |
TW583198B (en) | 2004-04-11 |
KR100478969B1 (ko) | 2005-03-24 |
EP1188775A2 (fr) | 2002-03-20 |
DE60114959D1 (de) | 2005-12-22 |
DE60114959T2 (de) | 2006-07-27 |
US6780931B2 (en) | 2004-08-24 |
JP2002167403A (ja) | 2002-06-11 |
CN1344750A (zh) | 2002-04-17 |
EP1188775A3 (fr) | 2002-10-09 |
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